Alkylphthalocyanine near-infrared absorbers and recording/display materials using the same

ABSTRACT

Near-infrared absorbers which contain phthalocyanine derivatives in which the four benzene rings contained in the molecule independently have 1 to 4 substituents are light and thermal resistant and possess high molar extinction coefficients. Such near-infrared absorbers are useful in optical recording media, near-infrared absorption filters, and liquid crystal display devices.

This is a continuation of application Ser. No. 07/660,937, filed on Feb.26, 1991, which is a division of application Ser. No. 07/593,255, filedOct. 1, 1990 (now U.S. Pat. No. 5,024,926), which is a continuation ofapplication Ser. No. 07/331,736, filed Apr. 3, 1989, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to alkylphthalocyanine near-infraredabsorbers. It also relates to recording and display materials fabricatedwith such near-infrared absorbers, including optical recording media(such as optical disks and optical cards), filters which absorb orscreen near-infrared radiation (such as goggles), and liquid crystaldisplay panels using near-infrared radiation.

2. Discussion of the Background

Near-infrared absorbers play an important role in optoelectronicapplications such as information recording media, display media,sensors, and goggles.

Conventionally known near-infrared absorbers include cyanine dyes(Japanese Patent Laid-Open Nos. 46221/'81 and 112790/'83),phthalocyanine dyes (Japanese Patent Laid-Open No. 36490/'83),naphthoquinone dyes (Japanese Patent Laid-Open No. 15458/'85),anthraquinone dyes (Japanese Patent Laid-Open No. 291651/'86), anddithiol complexes (Japanese Patent Laid-Open No. 175693/'83).

However, the previously known dyes suffer from major disadvantages.Specifically, cyanine dyes are insufficient in fastness properties suchas light resistance and thermal resistance. The absorption wavelengthranges of phthalocyanine dyes are as short as 600-700 nm. Anthraquinoneand naphthoquinone dyes have a low molar extinction coefficient, on theorder of several tens of thousands. Dithiol complexes are notsufficiently thermally stable and possess low molar extinctioncoefficients.

Thus, there remains a need for near-infrared absorbers which possess asufficient degree of fastness properties, such as light resistance,weather resistance, and thermal resistance, and sufficiently high molarextinction coefficients.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to providenear-infrared absorbers which absorb light in the near-infrared regionof 700 to 850 nm, have excellent light resistance, weather resistance,and thermal resistance and possess high molar extinction coefficients.

It is another object of the present invention to provide an opticalrecording medium containing such a near-infrared absorber in therecording layer thereof, a near-infrared absorption filter containingsuch a near-infrared absorber, and a display material comprising amixture of such a near-infrared absorber and a liquid crystal material.

These and other objects which will become apparent during the course ofthe following detailed description have been achieved by near-infraredabsorbers comprising a phthalocyanine derivative of the formula (I)##STR1## where R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶ independentlyrepresent hydrogen, alkyl, arylmethyl, alkoxymethyl, alkylthiomethyl,alkylaminomethyl, dialkylaminomethyl, aryloxymethyl, arylthiomethyl,arylaminomethyl, diarylaminomethyl, or alkylarylaminomethyl; R², R³, R⁶,R⁷, R¹⁰, R¹¹, R¹⁴, and R¹⁵ independently represent hydrogen, alkyl,arylmethyl, alkoxymethyl, alkylthiomethyl, alkylaminomethyl,dialkylaminomethyl, aryloxymethyl, arylthiomethyl, arylaminomethyl,diarylaminomethyl, alkylarylaminomethyl, alkylthio, arylthio, alkoxy,aryloxy, aryl, or halogen; and Met represents two hydrogen atoms, adivalent metal atom, a monosubstituted trivalent metal atom, adisubstituted tetravalent metal atom, or an oxymetal group.

In addition, the present invention also provides an optical recordingmedia containing the present near-infrared absorber in the recordinglayer thereof, near-infrared absorption filters containing the presentnear-infrared absorber, and display materials comprising a mixture ofthe present near-infrared absorber and a liquid crystal material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention will be more specifically described below inconnection with preferred embodiments.

Examples of the alkyl groups represented by R¹ to R¹⁶ in formula (I)include straight-chain, branched and cyclic hydrocarbon radicals having1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl,cyclohexyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, n-octyl, heptyl, andnonyl groups.

Among others, alkyl groups especially suitable for use as R¹, R⁴, R⁵,R⁸, R⁹, R¹², R¹³, and R¹⁶ are hydrocarbon radicals having 5 to 12 carbonatoms, such as n-amyl, isoamyl, neopentyl, n-hexyl, 2-ethylbutyl,n-heptyl, cyclohexylmethyl, n-octyl, 2-ethylhexyl, n-nonyl,3,5,5-trimethylhexyl, n-decyl, and 4-butylcyclohexylmethyl groups.

Examples of the arylmethyl groups represented by R¹ to R¹⁶ in formula(I) include benzyl groups having 0 to 5 substituents, such as benzyl,4-methylbenzyl, 4-ethylbenzyl, 4-propylbenzyl, 4-butylbenzyl,4-cyclohexylbenzyl, 2-ethylbenzyl, 2-hexylbenzyl, 3-butylbenzyl,methoxybenzyl, methylthiobenzyl, chlorobenzyl, and methylaminobenzylgroups; naphthylmethyl groups having 0 to 9 substituents, such as theethylnaphthylmethyl group; and heteroarylmethyl groups such assubstituted or unsubstituted thienylmethyl, furfuryl and indolylmethylgroups.

Among others, arylmethyl groups especially suitable for use as R¹, R⁴,R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶ are hydrocarbon radicals having 7 to 12carbon atoms, such as benzyl, 4-butylbenzyl and naphthylmethyl groups.

Examples of the alkoxymethyl groups include methyl groups having asubstituent selected from: straight-chain or branched hydrocarbonoxygroups having 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy,butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy groups;oligoethyloxy derivatives of the general formula R--(OCHY¹ CHY²)_(n)--O-- (where R represents a hydrogen atom or an alkyl group having 1 to6 carbon atoms, Y¹ and Y² independently represent a hydrogen atom,methyl group, chloromethyl group, or alkoxymethyl group, and n is aninteger of 1 to 5), such as methoxyethoxy, ethoxyethoxy, propoxyethoxy,butoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy,methoxyethoxyethoxyethoxy, hydroxyethyloxy, and hydroxyethoxyethoxygroups; alkylaminoalkoxy groups, such as N,N-dimethylaminoethoxy,N,N-diethylaminoethoxy, N,N-dimethylaminopropoxy groups; andalkylthioalkoxy groups, such as ethylthioethoxy, methylthioethoxy,phenylthioethoxy, methylthiopropoxy and ethylthiopropoxy groups.

Examples of the alkylthiomethyl groups include methyl groups having asubstituent selected from: straight-chain or branched hydrocarbonthiogroups having 1 to 30 carbon atoms, such as methylthio and ethylthiogroups; oligoalkoxyalkylthio groups such as methoxymethylthio,methoxyethylthio, ethoxyethylthio, butoxyethylthio, andmethoxyethoxyethylthio groups; oligoalkylthioalkylthio groups such asmethylthiomethylthio and ethylthioethylthio groups; alkylaminoalkylthiogroups such as N,N-dimethylaminoethylthio, N,N-diethylaminoethylthio,and N-methylaminopropylthio groups; and halogenated alkylthio groupssuch as chloroethylthio, bromoethylthio, iodoethylthio, fluoroethylthio,and dichloroethylthio groups.

Examples of the alkylaminomethyl and dialkylaminomethyl groups includemethyl groups having a substituent selected from: straight-chain orbranched alkyl-substituted amino groups having a total of 1 to 30 carbonatoms, such as methylamino, ethylamino, N,N-dimethylamino, andN,N-diethylamino groups; hydroxyalkylamino groups, such asN-(hydroxyethyl)amino and N,N-di(hydroxyethyl)amino groups;alkoxyalkylamino groups, such as N,N-di(methoxyethyl)amino,N,N-di(ethoxyethyl)amino and N,N-di(methoxyethoxyethyl)amino groups; andacyloxyalkylamino groups, such as the N,N-di(acetoxyethyl)amino group.

Examples of the aryloxymethyl groups include methyl groups having asubstituent selected from phenyloxy, naphthyloxy, alkylphenyloxy,alkylaminophenyloxy, halogen-substituted phenyloxy, nitrophenyloxy,alkoxyphenyloxy, and alkylthiophenyloxy groups.

Examples of the arylthiomethyl groups include methyl groups having asubstituent selected from phenylthio, naphthylthio, alkylphenylthio,aminophenylthio, alkylaminophenylthio, and alkoxyphenylthio groups.Examples of the arylaminomethyl and diarylaminomethyl groups includemethyl groups substituted with an amino group having one or twosubstituents selected from phenyl, alkylphenyl alkoxyphenyl,aminophenyl, dialkylaminophenyl, halophenyl, naphthyl, and heterocyclicaromatic groups. Examples of the alkylarylaminomethyl groups includemethyl groups substituted with an amino group having aromatic andaliphatic substituent groups, such as phenylmethylamino ornaphthylethylamino groups.

When the total number of carbon, oxygen, nitrogen, and sulfur atomspresent in each of the substituent groups represented by R¹, R⁴, R⁵, R⁸,R⁹, R¹², R¹³, and R¹⁶ is in the range of 5 to 12, the near-infraredabsorbers of the present invention have good solvent solubility, exhibithigh molar extinction coefficients in the solution phase, and can givecoating films having a high reflectance. Similarly, when the totalnumber of carbon, oxygen, nitrogen, and sulfur atoms present in each ofthe substituent groups represented by R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴, andR¹⁵ is in the range of 1 to 6, the near-infrared absorbers of thepresent invention give coating films having a high reflectance.

Examples of the divalent metal represented by Met include Cu, Zn,Fe(II), Co(II), Ni(II), Ru(II), Rh(II), Pd(II), Pt(II), Mn(II), Mg(II),Be(II), Ca(II), Ba(II), Cd(II), Hg(II), and Sn(II). Examples of themono-substituted trivalent metal include Al--Cl, Al--Br, Al--F, Al--I,Ga--Cl, Ga--F, Ga--I, Ga--Br, In--Cl, In--Br, In--I, In--F, Tl--Cl,Tl--Br, Tl--I, Tl--F, Al--C₆ H₅, Al--C₆ H₄ CH₃, In--C₆ H₅, In--C₆ H₄CH₃, In--C₁₀ H₇, and Mn(OH).

Examples of the disubstituted tetravalent metal include CrCl₂, SiCl₂,SiBr₂, SiBr₂, ZrCl₂, SiI₂, GeCl₂, GeBr₂, Gel₂, GeF₂, SnCl₂, SnBr₂, SnI₂,SnF₂, TiCl₂, TiBr₂, and TiF₂ ; Si(OH)₂, Ge(OH)₂, Zr(OH)₂, Mn(OH)₂, andSn(OH)₂ ; TiR₂, CrR₂, SiR₂, SnR₂, and GeR₂, where R is an alkyl, phenyl,or naphthyl group or a derivative thereof; Si(OR')₂, Sn(OR')₂, Ge(OR')₂,Ti(OR')₂, and Cr(OR')₂, where R' is an alkyl, phenyl, naphthyl,trialkylsilyl, dialkylalkoxysilyl, or acyl group or a derivativethereof; and Sn(SR")₂ and Ge(SR")₂, where R" is an alkyl, phenyl, ornaphthyl group or a derivative thereof.

Examples of the oxymetal group include VO, MnO, and TiO.

It is preferred that both of R¹ and R⁴, R⁵ and R⁸, R⁹ and R¹², or R¹³and R¹⁶ should not be hydrogen atoms.

When eight or more of the R¹ to R¹⁶ radicals are not hydrogen atoms, thecentral metal represented by Met preferably is vanadyl(IV) oxide becausethe resulting phthalocyanine derivatives absorb light in the wavelengthrange (750-850 nm) of semiconductor lasers. When four or more of the R¹to R¹⁶ radicals are not hydrogen atoms, a lead or manganese (III)derivative is preferred for the same reason.

Suitable manganese derivatives are manganese hydroxide derivatives ofthe general formula MnOY, such as Mn(OH), Mn[OSi(CH₃)₃ ], Mn[OSi(C₂ H₅)₃], Mn[OSi(C₃ H₇)₃ ], Mn[OSi(C₄ H₉)], Mn[OSi(C₈ H₁₇)₃ ], Mn[OSn(C₄ H₉)₃], Mn[OGe(CH₃)₃ ], Mn(OC H3), Mn(OC₆ H₅), Mn(OC₂ H₄ OC₂ H₄ OC₂ H₅), andMn[OC₂ H₄ N(CH₃)₂ ].

The near-infrared absorbers of the present invention, which fall withinthe scope of formula (I), can be synthesized as follows: One to fourintermediates are selected from the compounds represented by theformulas (II) and (III): ##STR2## in which the benzene ring may have oneor more substituent groups similar to those defined for formula (I). Theintermediate or intermediates are reacted with a metal derivative suchas a metal halide, acetate, or sulfate, for example, by heating in asolvent selected from urea, chloronaphthalene, halobenzenes,nitrobenzene, alcohols, and amino-alcohols.

In order to make optical recording media using a near-infrared absorberin accordance with the present invention, the near-infrared absorber maybe coated or vacuum-deposited onto a transparent substrate. According toone coating process, 0.05 to 20% by weight, preferably 0.5 to 20% byweight, of the near-infrared absorber and up to 20% by weight,preferably 0%, of a binder resin are dissolved in a solvent, and theresulting solution is applied to a substrate by means of a spin coater.According to one vacuum deposition process, the near-infrared absorberis deposited onto a substrate at a pressure of 10⁻⁷ to 10⁻⁵ torr and atemperature of 100° to 300° C.

The substrate for the recording medium may be formed of any opticallytransparent resin. Suitable resins include, for example, acrylic resins,polyethylene resin, vinyl chloride resin, vinylidene chloride resin,polycarbonate resins, ethylene resin, polyolefin copolymer resins, vinylchloride copolymer resins, vinylidene chloride copolymer resins, andstyrene copolymer resins.

Moreover, the substrate may be surface-treated with a thermosetting orultraviolet-curable resin.

Solvents suitable for coating purposes include, for example, halogenatedhydrocarbons such as dichloromethane, chloroform, carbon tetrachloride,tetrachloroethylene, and dichlorodifluoroethane; ethers such astetrahydrofuran, diethyl ether, and dibutyl ether; ketones such asacetone and methyl ethyl ketone; alcohols such as methanol, ethanol, andpropanol; cellosolves such as methyl cellosolve and ethyl cellosolve;and hydrocarbons such as hexane, cyclohexane, octane, benzene, toluene,and xylene.

In order to make near-infrared absorption filters using a near-infraredabsorber within the scope of formula (I), various methods may beemployed. For example, this can be accomplished by mixing a resin with acompound of formula (I) and molding the mixture; by pouring a mixture ofa resin monomer and a compound of formula (I) into a mold andpolymerizing the monomer; by dyeing a resin molding with a compound offormula (I); or by coating or vacuum-depositing a compound of formula(I) onto a surface of a substrate material.

As the base material of such filters, there may be used any transparentresin. Suitable resins include, for example, thermoplastic resins suchas polystyrene, polymethyl methacrylate, polycarbonates, polyethylene,and polypropylene; and thermosetting resins such as CR-39 (a product ofPPG, Ltd.), MR-3 and MR-6 (products of Mitsui-Toatsu Chemicals Co.,Ltd.).

Furthermore, display materials can be made by mixing a near-infraredabsorber of formula (I) with liquid crystal materials such as nematicliquid crystals, smectic liquid crystals, and cholesteric liquidcrystals. These display materials may be used in guest-host typedisplays, liquid crystal panels (in which a near-infrared absorber isincorporated in the liquid crystal and an image is written with a laserbeam), and the like.

Other features of the present invention will become apparent in thecourse of the following descriptions of exemplary embodiments which aregiven forillustration of the invention and are not intended to belimiting thereof.

EXAMPLES

In these examples, all parts are parts by weight.

Example 1

A reaction mixture composed of 72 parts of tetramethylphthalonitrile, 11parts of vanadium(III) chloride, 1 part of ammonium molybdate, and 1,000parts of 1-chloronaphthalene was heated under reflux at 220° C. for30hours. Thereafter, the reaction mixture was poured into 3,000 parts ofmethanol. The precipitated crystals were purified by columnchromatographyto obtain 30 parts of vanadyloxyhexadecamethylphthalocyanine. Its absorption maximum (λ_(max)) in CHCl₃was 732 nm.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   71.71         6.02    13.94                                          Found    71.02         5.91    14.01                                          ______________________________________                                    

Then, a 20 g/l chloroform solution of the same phthalocyanine derivativewas prepared. When this solution was spin-coated onto glass, theresultingfilm had a reflectance of 28% at 810 nm. Moreover, an opticalrecording medium was made by coating the above solution onto an opticaldisk substrate formed of a photopolymer. The resulting optical diskexhibited asensitivity of 50 dB when a record was made with a 780 nmlaser beam of 7 mW power (on the surface of the substrate) at arotational speed of 1,800 rpm. This optical disk had good stability toreproducing light and good storage stability.

Example 2

A liquid crystal panel was made by using an alkylcyanobiphenyl liquidcrystal material of the general formula ##STR3##(where R is an alkylgroup) and incorporating therein 0.7% by weight of thephthalocyaninederivative obtained in Example 1. For purposes of comparison, a liquidcrystal panel in which the phthalocyanine derivative was notincorporated was also made. For both liquid crystal panels, thethickness of the liquid crystal layer was 10 μm.

The liquid crystal panel of the present invention gave a greater writingline width than the conventional liquid crystal panel. When the laseroutput was 20 mW, the liquid crystal panel of the present inventionpermitted the light pen to write a line of 160 μm width at a light pentraveling speed of 2 cm/sec.

The same phthalocyanine derivative could be dissolved in thealkylcyanobiphenyl liquid crystal material at a concentration up toabout 2% by weight, and various weathering tests revealed that itpossesses a very long service life.

Specifically, the liquid crystal material containing the phthalocyaninederivative was placed into capsules, which were allowed to stand underdirect sunlight for 100 hours. Thereafter, the liquid crystal materialwastested for changes in absorbance and absorption spectrum, but nochanges were observed. Thus, this phthalocyanine derivative was found tobe very stable.

Example 3

One part of the phthalocyanine derivative obtained in Example 1 wasdissolved in 10 parts of chloroform, and this solution was coated onto aglass substrate to form a near-infrared absorption filter. This filterhadexcellent weather resistance.

Example 4

A reaction mixture composed of 72 parts of tetramethylphthalonitrile, 25parts of manganese(II) acetylacetonate, 70 parts of diazabicycloundecene(DBU), 1 part of ammonium molybdate, and 1,000 parts of diethyleneglycol was heated at 250° C. for 40 hours. Thereafter, the reactionmixture was poured into 10,000 parts of water containing 1,000 parts ofhydrochloric acid. The precipitated crystals were filtered off to obtain50 parts of hydroxymanganese(III) hexadecamethylphthalocyanine,Mn(OH)(C₃₂ N₈)(CH₃)₁₆.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   71.27         6.11    13.85                                          Found    71.30         6.09    13.55                                          ______________________________________                                    

A reaction mixture composed of 10 parts of the abovehydroxymanganese(III) hexadecamethylphthalocyanine, 25 parts oftriisopropylsilyl chloride, and 500 parts of pyridine was heated underreflux for 10 hours. Thereafter, the solvent was removed bydistillation, and the residue was extracted with chloroform. Thus, therewas obtained 8 parts of triisopropylsilyloxymanganese(III)hexadecamethylphthalocyanine. Its absorption maximum (λ_(max)) in CHCl₃was 800 nm.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   70.84         7.20    11.70                                          Found    69.98         7.02    11.50                                          ______________________________________                                    

One part of the above phthalocyanine derivative was dissolved in 100parts of benzene, and the resulting solution was spin-coated onto asubstrate toobtain an optical recording medium. When a record was madewith a 780 nm semiconductor laser beam, the optical recording mediumexhibited a C/N ratio of 60 dB at a power of 8 mW. No change wasobserved after the recordwas reproduced 1,000,000 times with a 0.5 mWlaser beam. Moreover, reproduction of the record was not interferredwith even after the opticalrecording medium was allowed to stand at atemperature of 80° C. anda relative humidity of 80% for 1,000 hours.

Moreover, 5 parts of the above phthalocyanine derivative was mixed with1,000 parts of polystyrene resin, and the resulting mixture washot-moldedto form a filter. This filter effectively absorbed light inthe wavelength range of 700 to 850 nm.

Example 5

A reaction mixture composed of 80 parts of 3-n-amylphthalonitrile, 25partsof manganese(II) acetylacetonate, 70 parts of DBU, 1 part ofammonium molybdate, and 1,000 parts of amyl alcohol was heated underreflux (at 138° C.) for 10 hours. Thereafter, the reaction mixture waspoured into 10,000 parts of water containing 1,000 parts of concentratedhydrochloric acid. The oily material which separated was extracted withbenzene and then washed with n-hexane to obtain 50 parts ofhydroxymanganese tetraamylphthalocyanine. Its absorption maximum(λ_(max)) in CHCl₃ was 740 nm.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   72.21         6.64    12.95                                          Found    71.95         6.32    13.01                                          ______________________________________                                    

A 10 g/l methanol solution of the same phthalocyanine derivative wasprepared. When this solution was coated onto an optical disk substrateformed of polycarbonate, the resulting optical disk had a reflectance of28% and exhibited good sensitivity.

Example 6

A reaction mixture composed of 80 parts of 3-n-amylphthalonitrile, 22partsof lead monoxide, and 1,000 parts of amyl alcohol was heated underreflux for 10 hours. Thereafter, the reaction mixture was poured intowater. The precipitated crystals were collected by filtration and thenpurified by column chromatography to obtain 20 parts of lead(II)tetraamylphthalocyanine. Its absorption maximum (λ_(max)) in CHCl₃ was730 nm.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   62.45         5.64    11.20                                          Found    62.10         5.53    11.30                                          ______________________________________                                    

An optical disk was made by spin-coating a 10 g/l n-octane solution ofthe same phthalocyanine derivative onto a polycarbonate substrate. Thisoptical disk had a reflectance of 30% at 780-830 nm. Moreover, itexhibited a sensitivity of 50 dB when a record was made with a 780 nmlaser beam of 7 mW power (on the surface of the substrate) at arotationalspeed of 1,800 rpm.

Example 7

Forty parts of tetra(p-tert-butylphenyloxymethyl)phthalonitrile, 5 partsofcopper acetate, and 10 parts of DBU were reacted by refluxing inchloronaphthalene. Thereafter, the reaction mixture was poured intomethanol. Thus, there was obtained 10 parts of copperhexadeca(p-tert-butylphenyloxymethyl)phthalocyanine. The results ofelemental analysis of the thus-obtained phthalocyanine derivative aregiven below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   78.77         7.63    3.53                                           Found    79.01         7.48    3.43                                           ______________________________________                                    

One part of the same phthalocyanine derivative was dissolved in 100parts of benzene, and the resulting solution was spin-coated onto asubstrate toobtain an optical recording medium. This optical recordingmedium exhibitedat C/N ratio of 60 dB and hence had good sensitivity.

Example 8

Ten parts of copper hexadecachlorophthalocyanine was reacted with 100partsof p-tert-butylbenzylmagnesium bromide to obtain 5 parts of copperhexadeca(p-tert-butylbenzyl)phthalocyanine. Its absorption maximum(λ_(max)) in CHCl₃ was 700 nm.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   85.71         5.59    5.55                                           Found    85.39         5.63    5.43                                           ______________________________________                                    

Example 9

Forty parts of tetra(p-tert-butylphenylthiomethyl)phthalonitrile wasreacted with 5 parts of vanadyl trichloride in chloronaphthalene.Thereafter, the reaction mixture was poured into methanol. Thus, therewasobtained 5 parts of vanadyloxyhexadeca(p-tert-butylphenylthiomethyl)phthalocyanine.

The results of elemental analysis of the thus-obtained phthalocyaninederivative are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   72.79         7.05    3.26                                           Found    72.50         6.97    3.00                                           ______________________________________                                    

Example 10

Twenty parts of 1-amyl-4-methylphthalocyanine was reacted with 3 partsof vanadium(III) trichloride by refluxing in 60 parts ofchloronaphthalene. Thereafter, the reaction mixture was poured into 300parts of methanol. The precipitate which formed was collected byfiltration, dried, and then purified by column chromatography (silicagel/toluene) to obtain 10 parts of vanadyloxytetraamyltetramethylphthalocyanine. Its absorption maximum (λ_(max)) intoluene was 720 nm.

The results of elemental analysis are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   73.42         7.04    12.23                                          Found    73.21         7.15    12.31                                          ______________________________________                                    

Ten parts of the same phthalocyanine derivative was dissolved in 1,000parts of dibutyl ether. This solution was coated onto an optical cardsubstrate formed of polycarbonate, and the coated surface was coveredwitha protective layer to obtain an optical card. On this optical card,a record could be made with a 780 nm semiconductor laser beam of 4 mWpower at a linear speed of 2 m/sec. As a result, the optical cardexhibited a C/N ratio of 50 dB. Moreover, this record could bereproduced with a 0.8 mW laser beam. The optical card was found to havegood stability to reproducing light, because the reproduction could berepeated 10⁵ times. Moreover, the optical card also had good storagestability.

Example 11

26.8 parts of 1,4-dihexylphthalonitrile was reacted with 3 parts ofvanadyl(III) trichloride by refluxing in chloronaphthalene for 3 hours.Thereafter, the reaction mixture was poured into 2,000 parts ofmethanol. The precipitated solid was collected by filtration, dried, andthen purified by column chromatography (silica gel/toluene) to obtain 15parts of vanadyloxy octahexylphthalocyanine. Its absorption maximum(λ_(max)) in toluene was 720 nm.

The results of elemental analysis are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   76.70         9.01    8.94                                           Found    77.01         8.93    8.87                                           ______________________________________                                    

Fifteen parts of the same phthalocyanine derivative was dissolved in1,000 parts of octane. This solution was spin-coated onto a substrate toobtain an optical disk. This optical disk had a reflectance of 35% at780 nm. Moreover, it exhibited a C/N ratio (or sensitivity) of 50 dBwhen a recordwas made with a 8 mW laser beam at a linear speed of 11m/sec. Furthermore,this optical disk had good stability to reproducinglight and good storage stability.

Example 12

36.4 parts of tetraamylphthalonitrile was reacted with 3 parts ofvanadium(III) trichloride by refluxing in 150 parts of chloronaphthalenefor 3 hours. Thereafter, the reaction mixture was poured into 3,000parts of methanol. The precipitated crystals were collected byfiltration, dried, and then purified by column chromatography (silicagel/toluene) to obtain 10 parts of vanadyloxyhexadecaamylphthalocyanine. Its absorption maximum (λ_(max)) in toluenewas 740 nm.

The results of elemental analysis are given below.

    ______________________________________                                               C (%)       H (%)   N (%)                                              ______________________________________                                        Calcd.   79.05         10.43   6.59                                           Found    78.95         10.13   6.49                                           ______________________________________                                    

For some of the compounds obtained in the foregoing examples, theabsorption maximum (λ_(max)) in solution and in film form, the maximumreflectance in film form, and the durability were evaluated. Thethus-obtained results are shown in Table 1. In addition, the results ofthree comparative examples in which conventional absorbers wereevaluated in the same manner are also shown in Table 1

                  TABLE 1                                                         ______________________________________                                                λ.sub.max                                                                       Maximum                                                                Solu-          reflectance.sup.f                                                                     Moisture                                                                             Thermal                                         tion.sup.d                                                                           Film.sup.f                                                                            (nm)/(%)                                                                              resistance                                                                           resistance                            ______________________________________                                        Compounds of                                                                  the present                                                                   invention                                                                     Example 1 732    745     800/29  ◯                                                                        ◯                         Example 4 800    810     850/26  ◯                                                                        ◯                         Example 5 740    752     780/31  ◯                                                                        ◯                         Example 11                                                                              720    760     800/35  ◯                                                                        ◯                         Conventional                                                                  absorbers                                                                     Comparative                                                                             806    820     830/15  ◯                                                                        ◯                         Example 1.sup.a                                                               Comparative                                                                             740    780     830/25  X      X                                     Example 2.sup.b                                                               Comparative                                                                              678.sup.e                                                                            710.sup.g                                                                             720/35.sup.g                                                                         ◯                                                                        ◯                         Example 3.sup.c                                                               ______________________________________                                         ◯ = good                                                         X = poor                                                                      Notes to Table 1:                                                              .sup.(a) An absorber which is described in Japanese Patent LaidOpen No.       25886/'86 (Example 1):                                                        ##STR4##                                                                      .sup.(b) An absorber which is described in Japanese Patent LaidOpen No.       112790/'83 (Example 3):                                                       ##STR5##                                                                      .sup.(c) An absorber which is described in Japanese Patent LaidOpen No.       36490/'83:                                                                    ##STR6##                                                                      .sup.(d) A chloroform solution.                                               .sup.(e) A chloronaphthalene solution.                                        .sup.(f) The light reflected from a spincoated film was measured at an        angle of 5°.                                                           .sup.(g) A film formed by vacuum evaporation.                            

Examples 13 to 79

In these examples, there were used a total of 52 intermediates(Intermediates 1 to 52 shown in Table 2) of the general formula (IV):##STR7##Using 1 to 4 of these intermediates, a variety of phthalocyaninederivatives were synthesized in the same manner as described in theforegoing examples. The intermediate(s), metal, and reaction conditionsused in each example, together with the absorption maximum (λ_(max)) ofthe resulting compound in solution, are shown in Table 3.

These near-infrared absorbers possess good compatibility with resins andgive optical recording media having high sensitivity and gooddurability. When used in filters, they exhibit desirable spectralcharacteristics. Moreover, they possess good compatibility with liquidcrystal compounds and give high contrast in liquid crystal displaydevices.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention maybe practiced otherwise than as specifically describedherein.

                                      TABLE 2                                     __________________________________________________________________________    Inter-                                                                        mediate                                                                            R.sup.1       R.sup.2    R.sup.3    R.sup.4                              __________________________________________________________________________     1   CH.sub.2 C.sub.6 H.sub.5                                                                    CH.sub.2 C.sub.6 H.sub.5                                                                 CH.sub.2 C.sub.6 H.sub.5                                                                 CH.sub.2 C.sub.6 H.sub.5              2   CH.sub.2 C.sub.6 H.sub.4 C(CH.sub.3).sub.3                                                  CH.sub.2 C.sub.6 H.sub.4 C(CH.sub.3).sub.3                                               CH.sub.2 C.sub.6 H.sub.4 C(CH.sub.3).sub.3                                               CH.sub.2 C.sub.6 H.sub.4                                                      C(CH.sub.3).sub.3                     3   CH.sub.2 SC.sub.6 H.sub.13 (n)                                                              CH.sub.2 SC.sub.6 H.sub.13 (n)                                                           CH.sub.2 SC.sub.6 H.sub.13                                                               CH.sub.2 SC.sub.6 H.sub.13 (n)        4   CH.sub.2 SC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                                 CH.sub.2 SC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                              CH.sub.2 SC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                              CH.sub.2 SC.sub.6 H.sub.4                                                     C(CH.sub.3).sub.3                     5   CH.sub.2 SC.sub.10 H.sub.7                                                                  CH.sub.2 SC.sub.10 H.sub.7                                                               CH.sub.2 SC.sub.10 H.sub.7                                                               CH.sub.2 SC.sub.10 H.sub.7            6   CH.sub.2 OC.sub.8 H.sub.17 (n)                                                              CH.sub.2 OC.sub.8 H.sub.17 (n)                                                           CH.sub.2 OC.sub.8 H.sub.17                                                               CH.sub.2 OC.sub.8 H.sub.17 (n)        7   CH.sub.2 OC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                                 CH.sub.2 OC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                              CH.sub.2 OC.sub.6 H.sub.4 C(CH.sub.3).sub.3                                              CH.sub.2 OC.sub.6 H.sub.4                                                     C(CH.sub.3).sub.3                     8   CH.sub.2 OC.sub.10 H.sub.7                                                                  CH.sub.2 OC.sub.10 H.sub.7                                                               CH.sub.2 OC.sub.10 H.sub.7                                                               CH.sub.2 OC.sub.10 H.sub.7            9   CH.sub.2 NHC.sub.6 H.sub.4 C.sub.8 H.sub.17                                                 CH.sub.2 NHC.sub.6 H.sub.4 C.sub.8 H.sub.17                                              CH.sub.2 NHC.sub.6 H.sub.4 C.sub.8 H.sub.17                                              CH.sub.2 NHC.sub.6 H.sub.4                                                    C.sub.8 H.sub.17                     10   CH.sub.2 N(C.sub.6 H.sub.5).sub.2                                                           CH.sub.2 N(C.sub.6 H.sub.5).sub.2                                                        CH.sub.2 N(C.sub.6 H.sub.5).sub.2                                                        CH.sub.2 N(C.sub.6 H.sub.5).sub.2                                             9                                    11   CH.sub.2 N(C.sub.4 H.sub.9).sub.2                                                           CH.sub.2 N(C.sub.4 H.sub.9).sub.2                                                        CH.sub.2 N(C.sub.4 H.sub.9).sub.2                                                        CH.sub.2 N(C.sub.4 H.sub.9).sub.2                                             4                                    12   CH.sub.2 NHC.sub.12 H.sub.25                                                                CH.sub.2 NHC.sub.12 H.sub.25                                                             CH.sub.2 NHC.sub.12 H.sub.25                                                             CH.sub.2 NHC.sub.12 H.sub.25         13   CH.sub.2 N(CH.sub.3)(C.sub.10 H.sub.7)                                                      CH.sub.2 N(CH.sub.3)(C.sub.10 H.sub.7)                                                   CH.sub.2 N(CH.sub.3)(C.sub.10 H.sub.7)                                                   CH.sub.2 N(CH.sub.3)(C.sub.10                                                 H.sub.7)                             14   CH.sub.2 C.sub.6 H.sub.4 C(CH.sub.3).sub.3                                                  H          H          CH.sub.2 C.sub.6 H.sub.4                                                      C(CH.sub.3).sub.3                    15   H             CH.sub.2 C.sub.6 H.sub.5                                                                 CH.sub.2 C.sub.6 H.sub.5                                                                 CH.sub.2 C.sub.6 H.sub.5             16   CH.sub.2 C.sub.6 H.sub.4 Cl                                                                 CH.sub.2 C.sub.6 H.sub.4 Cl                                                              CH.sub.2 C.sub.6 H.sub.4 OCH.sub.3                                                       CH.sub.2 C.sub.6 H.sub.4                                                      OCH.sub.3                            17   CH.sub.2 O(C.sub.2 H.sub.4 O).sub.3 H                                                       CH.sub.2 O(C.sub.2 H.sub.4 O).sub.3 H                                                    CH.sub.2 O(C.sub.2 H.sub.4 O).sub.3                                                      CH.sub.2 O(C.sub.2 H.sub.4                                                    O).sub.3 H                           18   CH.sub.2 O(C.sub.2 H.sub.4).sub.2 C.sub.2 H.sub.5                                           CH.sub.2 O(C.sub.2 H.sub.4).sub.2 C.sub.2 H.sub.5                                        CH.sub.2 O(C.sub.2 H.sub.4).sub.2 C.sub.2                                     H.sub.5    CH.sub.2 O(C.sub.2 H.sub.4).sub.2                                              C.sub.2 H.sub.5                     19   C.sub.5 H.sub.11 (iso)                                                                      CH.sub.3   CH.sub.3   C.sub.5 H.sub.11 (iso)               20   CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                 C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          CH.sub.2 CH(C.sub.2 H.sub.5)C.sub                                             .4 H.sub.9                           21   CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                 Cl         Cl         CH.sub.2 CH(C.sub.2                                                           H.sub.5)C.sub.4 H.sub.9              22   C.sub.5 H.sub.11 (iso)                                                                      SC.sub.6 H.sub.5                                                                         SC.sub.6 H.sub.5                                                                         C.sub.5 H.sub.11 (iso)               23   C.sub.6 H.sub.13 (n)                                                                        C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.13 (n)                 24   C.sub.6 H.sub.13                                                                            Cl         Cl         CH.sub.3                             25   C.sub.8 H.sub.17                                                                            CH.sub.3   CH.sub.3   C.sub.8 H.sub.17                     26   CH.sub.2 C.sub.6 H.sub.4 C(CH.sub.3).sub.3                                                  CH.sub.3   CH.sub.3   CH.sub.2 C.sub.6 H.sub.4                                                      C(CH.sub.3).sub.3                    27   C.sub.4 H.sub.9 (n)                                                                         H          H          C.sub.4 H.sub.9 (n)                  28   C.sub.6 H.sub.13 (n)                                                                        H          H          C.sub.6 H.sub.13 (n)                 29   C.sub.7 H.sub.15 (n)                                                                        H          H          C.sub.7 H.sub.15 (n)                 30   C.sub.2 H.sub.5                                                                             H          H          C.sub.2 H.sub.5                      31   CH.sub. 3     CH.sub.3   CH.sub.3   CH.sub.3                             32   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                      33   C.sub.7 H.sub.15 (n)                                                                        CH.sub.3   CH.sub.3   C.sub.7 H.sub.15 (n)                 34   C.sub.4 H.sub.9 (n)                                                                         CH.sub.3   CH.sub.3   C.sub.4 H.sub.9 (n)                  35   C.sub.2 H.sub.5                                                                             C.sub.3 H.sub.7 (iso)                                                                    C.sub.3 H.sub.7 (iso)                                                                    C.sub.2 H.sub.5                      36   CH.sub.3      C.sub.5 H.sub.11 (n)                                                                     C.sub.5 H.sub.11 (n)                                                                     CH.sub.3                             37   C.sub.5 H.sub.11                                                                            CH.sub.3   CH.sub.3   C.sub.5 H.sub.11 (n)                 38   CH.sub.2 CH[C(CH.sub.3).sub.3 ]CH.sub.2 CH.sub.2                                                       H          C.sub.5 H.sub.11 (iso)               39   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                                    H          C.sub.8 H.sub.17                     40   CH.sub. 3     CH.sub.3   CH.sub.3   C.sub.6 H.sub.13                     41   C.sub.3 H.sub.7                                                                             C.sub.3 H.sub.7 (n)                                                                      CH.sub.3   H                                    42   C.sub.8 H.sub.17                                                                            CH.sub.3   CH.sub.3   H                                    43   C.sub.5 H.sub.11                                                                            CH.sub.3   CH.sub.3   H                                    44   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          C.sub.5 H.sub.11                     45   C.sub.5 H.sub.11                                                                            C.sub.5 H.sub.11                                                                         C.sub.5 H.sub.11                                                                         H                                    46   C.sub.5 H.sub.11                                                                            C.sub.3 H.sub.7                                                                          C.sub.3 H.sub.7                                                                          H                                    47   C.sub.6 H.sub.13                                                                            C.sub.8 H.sub.17                                                                         C.sub.8 H.sub.17                                                                         H                                    48   C.sub.20 H.sub.41                                                                           CH.sub.3   CH.sub.3   C.sub.20 H.sub.41                    49                                                                                  ##STR8##     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                           ##STR9##                            50   CH.sub.2 C(CH.sub.3).sub.2 C(CH.sub.3).sub.3                                                H          H          H                                    51                                                                                  ##STR10##    H          H          H                                    52   n-C.sub.5 H.sub.11                                                                          H          H          H                                    __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________         Inter-                                                                   Example                                                                            mediate                                                                            Metal Reaction conditions                                                                             λ.sub.max                            __________________________________________________________________________    13   1    VO(acac).sub.2                                                                      Refluxed in chloronaphthalene.                                                                  730                                         14   1    CuCl  "                 770                                         15   1    Ni(OAc).sub.2                                                                       "                 710                                         16   1    Co(OAc).sub.2                                                                       "                 705                                         17   2    Ni(OAc).sub.2                                                                       "                 705                                         18   2    FeCl.sub.3                                                                          "                 708                                         19   2    VCl.sub.3                                                                           "                 735                                         20   2    H.sub.2                                                                             Reacted with metallic sodium in                                                                 725                                                         amyl alcohol and hydrolyzed with                                              hydrochloric acid.                                            21   1,3  VO(acac).sub.2                                                                      Reacted in urea at 200° C.                                                               735                                         22   1    SiCl.sub.4                                                                          Reacted in quinoline/tributyl-                                                                  710                                                         amine/DBU.                                                    23   1    SnCl.sub.4                                                                          Reacted in quinoline/tributyl-                                                                  730                                                         amine/DBU.                                                    24   1    The product of Example 22 was hydrolyzed.                                                             710                                         25   1    The product of Example 23 was hydrolyzed.                                                             720                                         26   1    The product of Example 22 was reacted with                                                            715                                                   PhMgBr.                                                             27   1    The product of Example 23 was reacted with                                                            715                                                   PhMgBr.                                                             28   1    The product of Example 24 was reacted with                                                            710                                                   trimethylsilyl chloride.                                            29   1    The product of Example 25 was reacted with                                                            710                                                   trimethylsilyl chloride.                                            30   1    GeCl.sub.4                                                                          Reacted in quinoline/tributyl-                                                                  710                                                         amine/DBU.                                                    31   1    The product of Example 30 was hydrolyzed.                                                             710                                         32   1    The product of Example 31 was reacted with                                                            710                                                   thiophenol.                                                         33   3    TiCl.sub.4                                                                          Reacted in quinoline/DBU.                                                                       710                                         34   3    AlCl.sub.3                                                                          "                 710                                         35   3    Cr(OAc).sub.3                                                                       "                 730                                         36   3    PdCl.sub.2                                                                          Refluxed in N,N-dimethylamino-                                                                  705                                                         ethanol.                                                      37   3    RhCl.sub.3                                                                          Refluxed in N,N-dimethylamino-                                                                  705                                                         ethanol.                                                      38   4    CuCl  Refluxed in N,N-dimethylamino-                                                                  715                                                         ethanol.                                                      39   6    "     Refluxed in N,N-dimethylamino-                                                                  715                                                         ethanol.                                                      40   7    "     Refluxed in N,N-dimethylamino-                                                                  715                                                         ethanol.                                                      41   8    "     Refluxed in N,N-dimethylamino-                                                                  715                                                         ethanol.                                                      42   9    "     Refluxed in N,N-dimethylamino-                                                                  725                                                         ethanol.                                                      43   10   "     Refluxed in N,N-dimethylamino-                                                                  725                                                         ethanol.                                                      44   11   "     Refluxed in N,N-dimethylamino-                                                                  725                                                         ethanol.                                                      45   12   "     Refluxed in N,N-dimethylamino-                                                                  725                                                         ethanol.                                                      46   1,2,3                                                                              "     Refluxed in N,N-dimethylamino-                                                                  710                                                         ethanol.                                                      47   18   "     Refluxed in N,N-dimethylamino-                                                                  715                                                         ethanol.                                                      48   14   Pb    Refluxed in N,N-dimethylamino-                                                                  750                                                         ethanol.                                                      49   15   PbO   Refluxed in amyl alcohol/DBU for                                                                740                                                         20 hours.                                                     50   16   Mn(acac).sub.2                                                                      Refluxed in amyl alcohol/DBU for                                                                750                                                         20 hours.                                                     51   17   VO(acac).sub.2                                                                      Refluxed in amyl alcohol/DBU for                                                                742                                                         20 hours.                                                     52   18   Mn(acac).sub.2                                                                      Reacted in ethylene glycol/DBU/                                                                 750                                                         ammonium molybdate at 200° C. for                                      20 hours.                                                     53   19   PbO   Reacted in ethylene glycol/DBU/                                                                 760                                                         ammonium molybdate at 200° C. for                                      20 hours.                                                     54   52   The product of Example 5 was reacted with                                                             740                                                   ClSi(C.sub.8 H.sub.17).sub.3.                                       55   21   VCl.sub.3                                                                           Refluxed in chloronaphthalene/                                                                  735                                                         ammonium molybdate for 20 hours.                              56   22   VCl.sub.3                                                                           Refluxed in chloronaphthalene/                                                                  775                                                         ammonium molybdate for 20 hours.                              57   23   VCl.sub.3                                                                           Refluxed in chloronaphthalene/                                                                  740                                                         ammonium molybdate for 20 hours.                              58   24   VCl.sub.3                                                                           Refluxed in chloronaphthalene/                                                                  735                                                         ammonium molybdate for 20 hours.                              59   25   Mn(acac).sub.2                                                                      Reacted in diethylene glycol/DBU/                                                               790                                                         ammonium molybdate at 250° C. for                                      30 hours.                                                     60   26   Mn(acac).sub.2                                                                      Reacted in diethylene glycol/DBU/                                                               790                                                         ammonium molybdate at 250° C. for                                      30 hours.                                                     61   27   Mn(acac).sub.2                                                                      Reacted in diethylene glycol/DBU/                                                               780                                                         ammonium molybdate at 250° C. for                                      30 hours.                                                     62   25   The product of Example 59 was reacted with                                                            791                                                   ClSn(C.sub.4 H.sub.9).sub.3.                                        63   26   The product of Example 60 was reacted with                                                            792                                                   ClSi(C.sub.3 H.sub.7).sub.3.                                        64   27   The product of Example 61 was reacted with                                                            788                                                   ClGe(CH.sub.3).sub.3.                                               65   28   VOCl.sub.2                                                                          Reacted in urea/ammonium molyb-                                                                 725                                                         date at 250° C. for 2 hours.                           66   29   VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   725                                                         ammonium molybdate at 220° C. for                                      20 hours.                                                     67   30   VO(acac).sub.2                                                                      Reacted in diethylene glycol/DBU                                                                725                                                         at 250° C. for 40 hours.                               68   31   VO(acac).sub.2                                                                      Reacted in diethylene glycol/DBU                                                                735                                                         at 250° C. for 40 hours.                               69   32   VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   740                                                         ammonium molybdate at 220° C.                          70   33,34                                                                              VO(acac).sub.2                                                                      Refluxed in amyl alcohol/DBU for                                                                740                                                         20 hours.                                                     71   35,36                                                                              VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   735                                                         ammonium molybdate at 250° C.                          72   37,40                                                                              VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   735                                                         ammonium molybdate at 250° C.                          73   38   VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   735                                                         ammonium molybdate at 250° C.                          74   39   VCl.sub.3                                                                           Reacted in chloronaphthalene/                                                                   735                                                         ammonium molybdate at 250° C.                          75   41,42                                                                              PbO   Reacted in diethylene glycol/DBU                                                                760                                                         at 250° C. for 30 hours.                               76   43,44                                                                              PbO   Reacted in diethylene glycol/DBU                                                                760                                              45,46      at 250° C. for 30 hours.                               77   48   PbO   Reacted in diethylene glycol/DBU                                                                780                                                         at 250° C. for 30 hours.                               78   50,51                                                                              Mn(acac).sub.2                                                                      Reacted in diethylene glycol/DBU                                                                765                                                         at 250° C. for 30 hours.                               79   49   Mn(acac).sub.2                                                                      Reacted in diethylene glycol/DBU                                                                790                                                         at 250° C. for 30 hours.                               __________________________________________________________________________

What is claimed as new and desired to be secured by Letters Patent ofthe United State is:
 1. A near-infrared absorber comprising aphthalocyanine derivative of formula (I): ##STR11## wherein R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ areindependently alkyl, arylmethyl, alkoxymethyl, alkylthiomethyl,alkylaminomethyl, dialkylaminomethyl, aryloxymethyl, arylthiomethyl,arylaminomethyl, diarylaminomethyl, or alkylarylaminomethyl, wherein thetotal number of carbon, oxygen, nitrogen, and sulfur atoms present ineach of R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶ is in the range of 5 to12; and Met is two hydrogen atoms, a divalent metal atom, amonosubstituted trivalent metal atom, a disubstituted tetravalent metalatom or an oxymetal group.
 2. The near-infrared absorber of claim 1,wherein the total number of carbon, oxygen, nitrogen and sulfur atomspresent in each of R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴, and R¹⁵ is in therange of 5 to
 12. 3. A near infrared absorber comprising aphthalocyanine derivative of formula (I): ##STR12## wherein the pairs ofR¹ and R⁴, R⁵ and R⁸, R⁹ and R¹², and R¹³ and R¹⁶, one of each pair isalkylthiomethyl, arylthiomethyl, arylaminomethyl, diarylaminomethyl oralkylarylaminomethyl, and the other is alkyl, arylmethyl,alkyloxymethyl, aryloxymethyl, alkylthiomethyl, arylthiomethyl,arylaminomethyl, diarylaminomethyl, or alkylarylaminomethyl, wherein thetotal number of carbon, oxygen, nitrogen and sulfur atoms present ineach of R¹, R⁴, R⁵, R⁸, R⁹, R², R¹³, and R¹⁶ is in the range of 5 to 12;R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴, and R¹⁵ are hydrogen atoms; and Met istwo hydrogen atoms, a divalent metal atom, a monosubstituted trivalentmetal atom, a disubstituted tetravalent metal atom or an oxymetal group.4. A near-infrared absorber comprising a phthalocyanine derivative offormula (I): ##STR13## wherein R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶independently are alkyl, arylmethyl, alkoxymethyl;, alkylthiomethyl,alkylaminomethyl, dialkylaminomethyl, aryloxymethyl, arylthiomethyl,arylaminomethyl, diarylaminomethyl, or alkylarylaminomethyl, wherein thetotal number of carbon, oxygen, nitrogen and sulfur atoms present ineach R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶ is in the range of 5 to 12;R², R³, R⁶, R⁷, R¹⁰, R¹¹, R¹⁴, and R¹⁵ independently are halogenalkylthio, arylthio, alkoxy, aryloxy or aryl; Met is two hydrogen atoms,a divalent metal atom, a monosubstituted trivalent metal atom, adisubstituted tetravalent metal atom or an oxymetal group.
 5. Anear-infrared absorber comprising the phthalocyanine derivative offormula (I): ##STR14## wherein R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶independently are branched alkyl or branched alkoxymethyl, wherein thetotal number of carbon and oxygen atoms present in each of R¹, R⁴, R⁵,R⁸, R⁹, R¹², R¹³, and R¹⁶ is in the range of 5 to 12; R², R³, R⁶, R⁷,R¹⁰, R¹¹, R¹⁴, and R¹⁵ are hydrogen atoms; and Met is two hydrogenatoms, a divalent metal atom, a monosubstituted trivalent metal atom, adisubstituted tetravalent metal atom or an oxymetal group.
 6. Anear-infrared absorber comprising a phthalocyanine derivative of formula(I): ##STR15## wherein R¹, R⁴, R⁵, R⁸, R⁹, R¹², R¹³, and R¹⁶independently are alkyl, arylmethyl or alkoxymethyl, wherein the totalnumber of carbon and oxygen atoms present in each of R¹, R⁴, R⁵, R⁸, R⁹,R¹², R¹³, and R¹⁶ is in the range of 5 to 12; R², R³, R⁶, R⁷, R¹⁰, R¹¹,R¹⁴, and R¹⁵ are hydrogen atoms; and Met is a monosubstituted trivalentmetal atom, a disubstituted tetravalent metal atom or an oxymetal group.